This invention relates to a grease composition, particularly a grease composition suitable for a constant velocity joint.
A constant velocity joint is used in a system for transmitting driving force, e.g., transmitting the force from a transmission gearbox to tires on a car. The constant velocity joint includes fixed type joints such as a Birfield joint, a Rzeppa joint and an undercutting free joint, and slide type joints such as a double off-set joint, a tripod joint and a cross groove joint.
A conventional grease which has been mainly used for such constant velocity joints contains a base grease consisting of a lubricating base oil and a lithium soap and/or urea thickener, and additives such as molybdenum disulfide and a lead compound.
The grease for the constant velocity joint is required to exhibit performances such as anti-flaking, anti-seizure, abrasion resistance, and low friction. However, the performance of the conventional grease hardly catches up with the tendency to improved performance and quality of recent cars. Thus, particularly in order to prolong the lifetime of a constant velocity joint, improvement of a grease in the anti-flaking property is desired.
The object of the present invention is to provide a grease composition for a constant velocity joint that exhibits superior anti-flaking performance.
According to the present invention, there is provided a grease composition comprising a lubricating base oil, and: (A) 2 to 30 wt % of a urea thickener, (B) 0.1 to 20 wt % of a sulfur-containing extreme pressure agent selected from the group consisting of dihydrocarbyl polysulfide, sulfurized oils and fats and mixtures thereof, and (C) 0.05 to 10 wt % of a sulfonate selected from the group consisting of an over-based zinc sulfonate, an over-based magnesium sulfonate and mixtures thereof having total base number of 100 to 500 mgKOH/g, each based on a total amount of said grease composition.
The present grease composition contains a lubricating base oil. The lubricating base oil may be a mineral oil and/or a synthetic oil. The kinematic viscosity of the lubricating base oil may be 2 to 40 mm2/s, and preferably 3 to 20 mm2/s at 100xc2x0 C. The viscosity index of the lubricating base oil may be not less than 90, and preferably not less than 100.
The mineral oil may be obtained by a conventional method commonly performed in a lubricating oil production process in oil refining industries. For example, the mineral oil may be obtained by preparing lubricant fractions of crude oil by distillation under atmospheric or reduced pressure, and then refining the lubricant fractions by at least one treatment selected from solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, contact dewaxing, hydrofining, washing with sulfuric acid, clay treatment, and the like.
Examples of the synthetic oil may include poly-xcex1-olefins such as polybutene, 1-octen oligomer and 1-decene oligomer, or hydrides of these poly-xcex1-olefins; diesters such as ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, or di-3-ethylhexyl sebacate; polyol esters such as trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethyl hexanoate, or pentaerythritol pelargonate; alkylnaphthalene; alkylbenzene; polyoxyalkylene glycol; polyphenyl ether; dialkyl diphenyl ether, silicone oil; and mixtures thereof.
The present grease composition contains (A) a specific content of a urea thickener. The component (A) may be a urea compound, a urea-urethane compound, a urethane compound or mixtures thereof.
Examples of the urea compound, urea-urethane compound and urethane compound may include a diurea compound, a triurea compound, a tetraurea compound, polyurea compounds other than diurea, triurea and tetraurea compounds, a urea-urethane compound, a diurethane compound and mixtures thereof. More specifically, any of compounds represented by the general formula (1) or mixtures thereof are preferable.
Axe2x80x94CONHxe2x80x94R1xe2x80x94NHCOxe2x80x94Bxe2x80x83xe2x80x83(1)
In the formula (1), R1 denotes a divalent hydrocarbon group. A and B are the same or different groups, and denote xe2x80x94NHR2, xe2x80x94NR3R, or xe2x80x94OR5. R2, R3, R4 and R5 are the same or different groups and denote a hydrocarbon residue having 6 to 20 carbon atoms.
Preferably, R1 in the formula (1) is a divalent hydrocarbon residue having 6 to 20, more preferably 6 to 15 carbon atoms. The divalent hydrocarbon group may be a straight or branched alkylene group, a straight or branched alkenylene group, a cycloalkylene group or an aromatic group. Specific examples of R1 may include an ethylene group, a 2,2-dimethyl-4-methylhexylene group and groups represented by the following formulae: 
Among these, the following groups are particularly preferred. 
R2, R3, R4 and R5 may be a straight or branched alkyl group, a straight or branched alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. Specific examples of R2, R3, R4 and R5 may include a straight or branched alkyl group such as a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, or an eicosyl group; a straight or branched alkenyl group such as a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group or an eicosenyl group; a cyclohexyl group; an alkylcycloalkyl group such as a methylcyclohexyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, a diethylcyclohexyl group, a propylcyclohexyl group, an isopropylcyclohexyl group, a 1-methyl-3-propylcyclohexyl group, a butylcyclohexyl group, an amylcyclohexyl group, an amylmethylcyclohexyl group, a hexylcyclohexyl group, a heptylcyclohexyl group, an octylcyclohexyl group, a nonylcyclohexyl group, a decylcyclohexyl group, an undecylcyclohexyl group, a dodecylcyclohexyl group, a tridecylcyclohexyl group or a tetradecylcyclohexyl group; an aryl group such as a phenyl group or a naphthyl group; an alkylaryl group such as a toluyl group, an ethylphenyl group, a xylyl group, a propylphenyl group, a cumenyl group, a methylnaphthyl group, an ethylnaphthyl group, a dimethylnaphthyl group or a propylnaphthyl group; or an arylalkyl group such as a benzyl group, a methylbenzyl group or an ethylbenzyl group. Among these, a cyclohexyl group, a octadecyl group, and a toluyl group are particularly preferred.
The diurea compound, the urea-urethane compound, or the diurethane compound may be prepared by reacting diisocyanate represented by the formula OCNxe2x80x94R1xe2x80x94NCO with a compound represented by the formula R2NH2, R3R4NH or R5OH or mixtures thereof in the base oil at 10 to 200xc2x0 C. In this case, R1, R2, R3, R4 and R5 are the same as those in the formula (1).
The lower limit of the content of the component (A) is 2 wt % and preferably 5 wt %; and the upper limit is 30 wt % and preferably 20 wt %, based on the total amount of the grease composition. If the content of the component (A) is less than 2 wt %, the component does not exhibit sufficient thickening effect, and the composition cannot thus be in a sufficiently greasy state. If the content of the component is more than 30 wt %, the composition becomes too hard as a grease to exhibit sufficient lubricating performance.
The present grease composition contains as component (B) a specific content of a sulfur-containing extreme pressure agent selected from the group consisting of dihydrocarbyl polysulfide, sulfurized oils and fats, and mixtures thereof.
The dihydrocarbyl polysulfide is a sulfur-containing compound which is generally called polysulfide or sulfurized olefin. Specifically, the dihydrocarbyl polysulfide may be represented by the formula (2);
R6xe2x80x94(S)x-R7xe2x80x83xe2x80x83(2)
wherein R6 and R7 may be the same or different groups, and each stands for a straight or branched alkyl group having 3 to 20 carbon atoms, or an aryl, alkylaryl or arylalkyl group having 6 to 20 carbon atoms. X stands for a number of 2 to 6, preferably 2 to 5. Examples of R6 and R7 may include a straight or branched alkyl group such as a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an icosyl group; an aryl group such as a phenyl group and a naphthyl group; an alkylaryl group such as a tolyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, a heptylphenyl group, an octylphenyl group, a nonylphenyl group, a decylphenyl group, an undecylphenyl group, a dodecylphenyl group, a xylyl group, an ethylmethylphenyl group, a diethylphenyl group, a dipropylphenyl group, a dibutylphenyl group, a methylnaphthyl group, an ethylnaphthyl group, a propylnaphthyl group, a butylnaphthyl group, a dimethylnaphthyl group, an ethylmethylnaphthyl group, a diethylnaphthyl group, a dipropylnaphthyl group and a dibutylnaphthyl group, including all of the structural isomers; and an arylalkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group, including all of the structural isomers.
Among these, each of R6 and R7 of the formula (2) may preferably be an alkyl group derived from a propylene, a 1-butene or an isobutylene and having 3 to 18 carbon atoms, or an aryl, alkylaryl or arylalkyl group having 6 to 8 carbon atoms. Specifically, an alkyl group such as an isopropyl group, branched hexyl groups derived from propylene dimers, branched nonyl groups derived from propylene trimers, branched dodecyl groups derived from propylene tetramers, branched pentadecyl groups derived from propylene pentamers, branched octadecyl groups derived from propylene hexamers, a sec-butyl group, a tert-butyl group, branched octyl groups derived from 1-butene dimers, branched octyl groups derived from isobutylene dimers, branched dodecyl groups derived from 1-butene trimers, branched dodecyl groups derived from isobutylene trimers, branched hexadecyl groups derived from 1-butene tetramers and branched hexadecyl groups derived from isobutylene tetramers, including all of branched isomers; an alkylaryl group such as a phenyl group, a tolyl group, an ethylphenyl group and a xylyl group, including all of branched isomers; and an arylalkyl group such as a benzyl group and a phenylethyl group, including all of isomers, are preferable.
Particularly, each of R6 and R7 in the formula (2) may preferably be a branched alkyl group derived from propylene or isobutylene and having 3 to 18 carbon atoms. A branched alkyl group derived from propylene or isobutylene and having 6 to 15 carbon atoms is further preferable.
The content of sulfur in the dihydrocarbyl polysulfide may usually be 10 to 55 wt %, and preferably 20 to 50 wt % for obtaining an excellent extreme-pressure performance, although not limited thereto.
The sulfurized oils and fats for the component (B) may be animal or vegetable oils and fats such as beef tallow, lard, fish oil, rapeseed oil and soybean oil; unsaturated fatty acids such as oleic acid, linolic acid, linolenic acid and fatty acids extracted from the animal or vegetable oils and fats; unsaturated fatty acid esters obtained by reacting the unsaturated fatty acids or acid halides thereof with various alcohols; or mixtures thereof, that naturally contain sulfur, or that have been sulfurized by any methods.
The content of sulfur in the sulfurized oils and fats may usually be 2 to 40 wt %, and preferably 5 to 35 wt % for obtaining an excellent extreme-pressure performance, although not limited thereto.
The lower limit of the content of the component (B) is 0.1 wt % and preferably 0.5 wt %; and the upper limit is 20 wt % and preferably 10 wt %, based on the total amount of the grease composition. If the content of the component (B) is less than 0.1 wt %, the composition cannot exhibit sufficient anti-seizure performance. Addition of more than 20 wt % of the component does not result in further improvement in anti-seizure performance that meets the adding amount.
The present grease composition contains (C) a specific content of a sulfonate selected from the group consisting of an over-based zinc sulfonate, an over-based magnesium sulfonate and mixtures thereof. The lower limit of total base number of the component (C) is 100 mgKOH/g and preferably 150 mgKOH/g; and the upper limit is 500 mgKOH/g and preferably 450 mgKOH/g. If the total base number of the component (C) is less than 100 mgKOH/g, sufficient synergistic effect of components (B) and (C) in the anti-flaking performance cannot be achieved. The component (C) having the total base number of more than 500 mgKOH/g is not readily available.
The term xe2x80x9ctotal base numberxe2x80x9d in the present invention means the total base number measured by perchloric acid method in accordance with item 7. in JIS K 2501 xe2x80x9cPetroleum Products and Lubricantsxe2x80x94neutralization value test methodxe2x80x9d.
The component (C) may preferably be an over-based oil-soluble sulfonate selected from the group consisting of an over-based oil-soluble zinc sulfonate, an over-based oil-soluble magnesium sulfonate and mixtures thereof. The examples of such over-based oil-soluble sulfonate may include an over-based oil-soluble zinc sulfonate containing calcium carbonate, an over-based oil-soluble zinc sulfonate containing calcium borate, an over-based oil-soluble magnesium sulfonate containing magnesium carbonate, an over-based oil-soluble magnesium sulfonate containing magnesium borate, and mixtures thereof.
The over-based oil-soluble zinc sulfonate containing calcium carbonate may be prepared by any method. For example, it may be prepared by dispersing a calcium base (such as oxides or hydroxides of calcium) in a neutral zinc sulfonate (normal salt), and blowing carbon dioxide gas into the dispersion, so that the carbon dioxide gas and the calcium base react to generate a calcium carbonate dispersion in the system.
The over-based oil-soluble zinc sulfonate containing calcium borate may be prepared by any method. For example, it may be prepared by dispersing a calcium base (such as oxides or hydroxides of calcium) in a neutral zinc sulfonate (normal salt), and adding boric acid, a salt of boric acid or an ester of boric acid to the system, to generate a calcium borate dispersion in the system; or by reacting the over-based oil-soluble zinc sulfonate containing calcium carbonate with boric acid, a salt of boric acid or an ester of boric acid, to convert the calcium carbonate dispersed in the system to calcium borate.
The over-based oil-soluble magnesium sulfonate containing magnesium carbonate may be prepared by any method. For example, it may be prepared by dispersing a magnesium base (such as oxides or hydroxides of magnesium) in neutral magnesium sulfonate (normal salt), and blowing carbon dioxide gas into the system, so that the carbon dioxide gas and the magnesium base react to generate a magnesium carbonate dispersion in the system.
The over-based oil-soluble magnesium sulfonate containing magnesium borate may be prepared by any method. For example, it may be prepared by dispersing a magnesium base (such as oxides or hydroxides of magnesium) in neutral magnesium sulfonate (normal salt), and adding boric acid, a salt of boric acid or an ester of boric acid to the system, to generate a magnesium borate dispersion in the system; or by reacting the over-based oil-soluble magnesium sulfonate containing magnesium carbonate with boric acid, a salt of boric acid or an ester of boric acid, to convert the magnesium carbonate dispersed in the system to magnesium borate.
These reactions may usually be performed in a solvent, for example, an aliphatic hydrocarbon solvent such as hexane; an aromatic hydrocarbon solvent such as xylene; or a light lubricating base oil.
Examples of the boric acid for producing the over-based oil-soluble zinc sulfonate containing calcium borate or the over-based oil-soluble magnesium sulfonate containing magnesium borate may include orthoboric acid, metaboric acid and tetraboric acid. Examples of the salt of boric acid may include an alkali metal salt, an alkali earth metal salt or an ammonium salt of boric acid. Specifically, lithium borates such as lithium metaborate, lithium tetraborate, lithium pentaborate, lithium perborate; sodium borates such as sodium metaborate, sodium diborate, sodium tetraborate, sodium pentaborate, sodium hexaborate. and sodium octaborate; potassium borates such as potassium metaborate, potassium tetraborate, potassium pentaborate, potassium hexaborate and potassium octaborate; calcium borates such as calcium metaborate, calcium diborate, tricalcium tetraborate, pentacalcium tetraborate and calcium hexaborate; magnesium borates such as magnesium metaborate, magnesium diborate, trimagnesium tetraborate, pentamagnesium tetraborate, magnesium hexaborate; and ammonium borates such as ammonium metaborate, ammonium tetraborate, ammonium pentaborate and ammonium octaborate are preferable.
Examples of the ester of boric acid may include esters of boric acid and alkyl alcohols preferably having 1 to 6 carbon atoms. Specifically, monomethyl borate, dimethyl borate, trimethyl borate, monoethyl borate, diethyl borate, triethyl borate, monopropyl borate, dipropyl borate, tripropyl borate, monobutyl borate, dibutyl borate and tributyl borate are preferable.
Examples of the neutral zinc sulfonate (normal salt) for producing the over-based oil-soluble zinc sulfonate may include a zinc natural salt of an alkyl aromatic sulfonic acid which has been produced by sulfonation of an alkyl aromatic compound having a weight average molecular weight of 100 to 1500, preferably 200 to 700. The alkyl aromatic sulfonic acid may be petroleum sulfonic acid or synthetic sulfonic acid.
Examples of the neutral magnesium sulfonate (normal salt) for producing the over-based oil-soluble magnesium ulfonate may include a magnesium natural salt of an alkyl aromatic sulfonic acid which has been produced by sulfonation of an alkyl aromatic compound having a weight average molecular weight of 100 to 1500, preferably 200 to 700. The alkyl aromatic sulfonic acid may be petroleum sulfonic acid or synthetic sulfonic acid.
The petroleum sulfonic acid may be a sulfonated product of an alkyl aromatic compound from lubricant fractions of a mineral oil, or so called mahogany acid, which is a by-product of white oil. The synthetic sulfonic acid may be a sulfonated product of alkylbenzene having straight or branched alkyl group(s), or a sulfonated product of alkylnaphthalene. The alkylbenzene may be a by-product produced in a plant for manufacturing alkylbenzene as a material for detergent, or an alkylated product of benzene with polyolefin. The alkylnaphthalene may be dinonylnaphthalene. There is no limitation to the sulfonating agent for sulfonating the alkyl aromatic compounds. However, fuming sulfuric acid or sulfuric anhydride may usually be used.
As the component (C), commercially available products in a diluted form with light lubricating base oil may also be used.
The content of zinc and/or magnesium in the component (C) is not particularly limited. However, the total content of zinc and/or magnesium in the component (C) may be 0.5 to 30 wt %, preferably 1 to 25 wt %, and more preferably 1 to 20 wt %, for synergistic anti-flaking effect in the present composition.
The lower limit of the content of the component (C) is 0.05 wt % and preferably 0.1 wt %; and the upper limit is 10 wt % and preferably 5 wt %, based on the total amount of the grease composition. If the content of the component (C) is less than 0.05 wt %, sufficient synergistic effect of the components (B) and (C) cannot be achieved in the anti-flaking performance. Addition of more than 10 wt % of the component (C) does not result in further improvement in anti-flaking performance that meets the adding amount.
If necessary, the present grease composition may contain other additives for further improving the properties, as long as such other additives do not damage the properties of the grease composition.
Examples of such other additives may include a solid lubricant, an extreme pressure agent other than the component (B), an anti-oxidant, an oiliness agent, a rust-inhibitor, and a viscosity index improver.
Examples of the solid lubricant may include graphite, fluorinated graphite, boron nitride, polytetrafluoroethylene, molybdenum disulfide, antimony sulfide, and alkali or alkali earth metal borate.
Examples of the extreme pressure agent other than the component (B) may include organozinc compounds such as zinc dialkyl dithiophosphate, zinc diaryl dithiophosphate and zinc dialkyl dithiocarbamate; organomolybdenum compounds such as molybdenum dialkyl dithiophosphate, molybdenum diaryl dithiophosphate and molybdenum dialkyl dithiocarbamate; thiocarbamyl compounds; and phosphates and phosphites.
Examples of the anti-oxidant may include phenol compounds such as 2,6-di-t-butylphenol and 2,6-di-t-butyl-p-cresol; amine compounds such as dialkyldiphenylamine, phenyl-xcex1-naphthylamine and p-alkylphenyl-xcex1-naphthylamine; sulfur compounds; and phenothiazine compounds.
Examples of the oiliness agent may include amines such as lauryl amine, myristyl amine, palmityl amine, stearyl amine and oleyl amine; higher alcohols such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and oleyl alcohol; higher fatty acids such as layric acid, myristic acid, palmitic acid, stearic acid and oleylic acid; fatty acid esters such as methyl laurate, methyl myristate, methyl palmitate, methyl stearate and methyl oleate; amides such as lauryl amide, myristyl amide, palmityl amide, stearyl amide and oleyl amide; and oils and fats.
Examples of the rust-inhibitor may include metal soaps; partial esters of polyalcohols such as sorbitan fatty acid ester; amines; phosphoric acid; and phosphates.
Examples of the viscosity index improver may include polymethacrylate, polyisobutylene and polystylene.
The grease composition of the present invention may be produced, for example, by adding the components (A) to (C) and optionally other additives to the lubricating base oil, agitating the resulting mixture, and passing the mixture through a roll mill. Alternatively, the grease composition of the present invention may be produced by preparing the thickener component (A) in a lubricating base oil in advance, further adding the components (B) and (C) and other optional additives to the mixture, agitating the resulting mixture, and passing the mixture through the roll mill. The preparation of the component (A) in the lubricating base oil may be performed by adding materials for producing the thickener component (A) to the lubricating base oil, and melting and agitating the mixture.
The grease composition of the present invention has excellent anti-flaking property, anti-seizure property and low-friction property, and is therefore useful as a grease for, e.g., a constant velocity gear, a speed-change gear and an iron manufacturing plant. Particularly, the grease composition of the present invention is useful for constant velocity joints including fixed type joints such as a Birfield joint, a Rzeppa joint and an undercutting free joint, and slide type joints such as a double off-set joint, a tripod joint and a cross groove joint.